Synergistic fungicidal composition



United States Patent Int. Cl. A0111 9/02, 9/12 US. Cl. 424-274 12 Claims ABSTRACT OF THE DISCLOSURE Synergistic combination of zinc propylene-1,2-bis-dithiocarbamate and N-trichloromethylthiophthalimide which possesses outstanding fungicidal properties.

The present invention relates to and has for its objects the provision for a particular new synergistic combination of zinc propylene-1,2-bis-dithiocarbamate and N- trichlorornethylthiophthalimide, both of which are known, which combination possesses outstanding fungicidal properties, active compositions in the form of synergistic mixtures of such two compounds with solid and liquid dispersible carrier vehicles, and methods for using such two compounds synergistically in a new way especially for combating fungi, with other and further objects becoming apparent from a study of the within specification and accompanying examples.

It is known that zinc propylene-1,2-bis-dithiocarbamate (Ia) can be used for the control of phytopathogenic fungi. This active compound has already attained a considerable importance in practice and is used for the control of various fungi, for example downy mildew fungi. Such compound suffers from the disadvantage, however, that it possesses only a weak fungicidal activity against Botrytis.

It is also known that N-trichloromethylthiophthalimide (Ila) can be used for the control of phytopathogenic fungi. This active compound also has attained a considerable importance in practice. For example, it too is used with good results against downy mildew fungi. This compound also has the disadvantage that it possesses only a weak fungicidal activity against Botrytis.

In this regard, it is generally known and accepted that Botrytis is very difficult to control fungistatically with chemical agents.

It has been found, in accordance with the present invention, that particular new compositions which comprise syngergistic mixture combinations of the two active compounds: zinc propylene-1,Z-bis-dithiocarbamate having the formula ICC and N-trichloromethylthiophthalimide having the formula N-scon o II preferably in a weight ratio of substantially between about 1:0.25 and 1:2, possess especially broad and selective fungicidal activity.

Surprisingly, the fungicidal effectiveness of this combination of said two active compounds is much higher than the sum of the activities of the individual active compounds. A genuine synergistic effect is therefore present. A great advantage of the combination is that it acts both against the normal phytopathogenic fungi and also against the Botrytis species which are usually particularly difiicult to control.

The weight ratio of the two compounds in the synergistic compositions can be varied within certain ranges. In general, the composition mixture contains 0.25-2, for example 0.5-2, preferably 0.7-1.5, parts by weight of N-trichloromethylthiophthalimide (IIa) to 1 part by weight of zinc propylene-1,2-bis-dithiocarbamate (Ia).

The instant compositions show a synergistic fungicidal effect in the case of phytopathogenic fungi, but in particular on Botrytis species.

The instant compositions can therefore be used for the control of phytopathogenic fungi, preferably for the control of Botrytis species. Particularly important in practice is the control of plant diseases which are caused by Botrytis, and plant diseases which occur at the same time and are caused by other phytopathogenic fungi. Thus, the instant synergistic compositions are suitable for example both for the control of Botrytis cinerea and Plasmopam viticola.

The instant synergistic compositions are usable in particular for Botrytis control in viticulture. Botrytis 4 cinerea may infest all parts of the vine. Most important economically are the infestation of the berries (berry rot) and grape stems (common grey mould). At the time of vine blossom, the fungus may also infest the young grapes (inflorescence Botrytis) and cause considerable damage as a result. Moreover, Botrytis diseases also occur in fruit cultivation, for example in strawberries; in ornamental plant cultivation, for example in all bulbous plants; in vegetable cultivation, for example in onions; and in coffee cultivation, and the like.

When the instant composition is used for the control of Botrytis, it also evinces an acaricidal activity against spider mites. This side-effect is in many cases very important because it keeps spider mite infestation under control.

The particular synergistic mixture combinations of active compounds to be used according to the instant invention can be utilized, if desired, in the form of the usual formulations or compositions with diluents or extenders, i.e.,- dispersible carrier vehicles, such as solutions, emulsions, suspension, ernulifiable concentrates, spray powders, pastes, soluble powders, dusting agent, ganulates, etc. These are prepared in known manner, for instance by extending the active compounds with dispersible liquid diluent carriers and/or dispersible solid carriers optionally with the use of carrier vehicle assistants, e.g., surfaceactive agents, including emulsifying agents and/or dispersing agents, whereby, for example, in the case where water is used as diluent, organic solvents may be added as auxiliary solvents (cf. Agricultural Chemicals, March 1960, pages 35-38). The following may be chiefly considered for use as carrier vehicles for this purpose: dispersible liquid diluent carriers, such as aromatic hydrocarbons (for instance, benzene, tolene, xylene, etc.), halogenated, especially chlorinated, aromatic hydrocarbons (for instance, chlorobenzenes), paraflins (for instance, petroleum fractions), chlorinated aliphatic hydrocarbons (for instance, methylene chloride, etc.), alcohols (for instance, methanol, ethanol, propanol, butanol, etc.), amines (for instance, ethanolamine, etc.), ethers, etheralcohols (for instance, glycol monomethyl ether, etc.) amides (for instance, dimethyl formamide, etc.), sulfoxides (for instance, dimethyl sulfoxide, etc.), ketones (for instance, acetone, etc.), and water; as well as dispersible finely divided solid carriers, such as ground natural minerals (for instance, kaolins, alumina, silica, chalk, i.e., calcium carbonate, talc, kieselguhr, etc.) and ground synthetic minerals (for instance, highly dispersed silicic acid, silicates, e.g., alkali silicates, etc.); whereas the following may be chiefly considered for use as carrier vehicle assistants, e.g., surface-active agents, for this purpose: emulsifying agents, such as non-ionic and anionic emulsifying agents (for instance, polyethylene oxide esters of fatty acids, polyethylene oxide ethers of fatty alcohols, alkyl sulfonates, aryl sulfonates, etc., and especially alkyl aryl-poly-gylcol ethers, magnesium stearate, sodium oleate, etc.); and dispersing agents, such as lignin, sulfite waste liquors, methyl cellulose, etc.

As will be appreciated 'by the artisan, the synergistic mixture of active compounds according to the instant invention may be employed alone or in the form of overall extended mixtures with such solid or liquid dispersible carrier vehicles and/or with other known compartible active agents, especially plant protection agents, such as other fungicides, herbicides, insecticides, bactericides, etc., if desired, or in the form of particular dosage preparations for specific application made therefrom, such as solutions, emulsions, suspensions, powders, pastes, and granulate which are thu ready for use, e.g. for application to agricultural crops such as in viticulture.

As concerns commercially marketed preparations, these generally contemplate carrier composition overall mixtures in which the synergistic mixture of active compounds is present in a combined total amount substan tially between about 01-95%, and preferably O.590% by weight of the overall extended mixture, whereas carrier composition mixtures suitable for direct application or field application generally contemplate those in which the synergistic mixture of active compounds is present in a combined total amount substantially between about 0.01-0.5%, preferably 0.030.2%, by weight of the overall extended mixture. Thus, the present invention contemplates over-all compositions which comprise extended mixtures of a dispersible carrier vehicle such as (1) a dispersible carrier solid, or (2) a dispersible carrier liqiud preferably including a carrier vehicle assistant, e.g., surface-active agent, such as an emulsifying agent and/or a dispersing agent, and a combined total amount of the synergistic mixture of active compounds which is effective for the purpose in question and which is generally about 0.0l95%, and preferably 0.0395%, by weight of the overall extended mixture.

Furthermore, the present invention contemplates methods of selectively controlling or combating fungi, especially Botrytis species, which comprises applying to at least one of (a) such fungi and (b) their habitat, i.e. the locus to 'be protected, a fungicidally effective amount of the particular synergistic mixture of said two active compounds of the invention alone or together in an overall mixture with a carrier vehicle as noted above. The instant formulations or compositions are applied in the usual manner, for instance by spraying, atomizing, vaporizing, scattering, dusting, watering, sprinkling, pouring, and the like.

In general, such synergistic mixture of said two active compounds is used, i.e. applied, in a combined total amount of substantially between about 0.0110, preferably 1.53.0, kilograms per hectare, regardless of the presence or absence of the carrier vehicle and/or other compatible active agents.

It will be realized, of course, that the concentration of the particular synergistic mixture of said two active compounds utilized in admixture with the carrier vehicle will depend upon the intended application, and such concentration may be varied within fairly wide limits. Therefore, in special cases, it is possible to go above or below the aforementioned concentration ranges.

The outstanding fungitoxic effectiveness of the synergistic mixture of said two active compounds according to the present invention, as well as their distinct superiority compared with the use of such particular active compounds separately, can be seen, by way of illustration and without limitation, from the following experimental test results:

EXAMPLE 1 Botrytis test The ready-to-use preparations of the particular active compound or synergistic mixture were prepared by diluting with water a concentrate of such active compound or synergistic mixture (i.e. consisting of 70% of active compound or synergistic combination of active compounds [zinc propylene-1,2-bis-dithiocarbamate (Ia) and N- trichloromethylthiophthalimide (IIa)] in the ratio of 110.7, 26% of silicic acid powder as inert material, 2.5% of lignin sulfate as protective colloid and 1.5% of alkylaryl surfonate as adhesive) until the desired active compound concentration was reached.

Vines were sprayed with these aqueous preparations of the given active compound or compounds 8 times (at an interval of 2 weeks in each case), during the entire vegetation period, that is during the season from the middle of May until the middle of September.

For each individual experiment, plots with about 50 vines were used. In each case, 4 somewhat differently lying plots were treated in the same manner in order to obtain a sufliciently exact average value in the evaluation.

Beside the treated plots, control plots were also established which were not active compound treated.

All the plots were infested by Botzytis cinerea in the course of the vegetation period. 4 weeks after the occurrence of the first symptoms, the extent of inflorescence Botrytis was determined, while the extent of berry rot and that of common grey mould were determined in each case 2-3 days before harvesting.

In each case the infestation of the treated vines in the individual plots was determined as a percentage of the infestation of the untreated vines. 0% therefore means no infestation, whereas means that the treated vines are exactly as infested as the untreated vines. The particular active compounds, the concentrations of such active compounds and the degrees of infestation can be seen from the following Table 1a, 1b and 1c.

TABLE la.INFLORESCENCE BOTRYTIS Goncentra Infestation tion of as percentactlve age of the compounds untreated Active compounds in percent control Control i. 100 In (alone) Zinc-propylene-1,2-bis-dithioearbamate--. 0. 14 59 Ila (alone) N-trichlorornethyl-tliipohthalimide 0. 1 32 1a Zinc-propylene-1,2-bisdithiocarbalnate-... 0.07

plus and 17 Ila (together) N-trichloromethyl-thiophthalimide 0.05

TABLE 1b.-BERRY ROT Infestation as Concentrapercentage of tion of the untreated active control compounds Active compounds in percent (a) (b) (0) Control 0 100 100 100 Ia (alone) Zinc-propylene-l,2-bis-dithiocarbamate.... 0.14 69 50 31 Ha (alone) N-trichloromethyLthiophthalimide 0.1 53 33 29 Ia Zinc-propylene-l,2-bis-dithiocarbamate. 0.07

plus and 38 8 6 11a (together) Nt1iohloromethyl-thiophthalimide 0.05

1 3 experiments in different regions of Germany.

TABLE 1c.COMMON GREY MOULD Concentra- Infestation tion of as percentactive age of the compounds untreated Active compounds in percent control Control- L 0 100 Ia (alone) Zinc-propylene 1,2-bis-dithiocarbamate.... 014 75 Ila (alone) N-trichloromethyl-thiophthalimide 0. 1 73 Is Zinc-propylened,2-bis-dithiocarbarnate. i 0.07

plus and 47 Ha (together) N-trichlorometliyl-thiophthalim1de 0.05

EXAMPLE 2 lings is determined as a percentage of the untreated but also inoculated control plants Fusicladlum test a le scab Protective pp 1 0% means no infestation; 100% means that the infes- Parts by Wt. 0 tatlon is exactly as great as in the case of the control Solvent, acetone 4-7 plants. Emulsifier, alkylaryl polyglycol ether The particular active compounds, the concentrations f Water ch actlve compounds and the results obtai d can be The amount of the particular active compound or seen from the following Table 2:.

TABLE 2.-FUSICLADIUM TEST (PROTECTIVE) Active compound Ia (alone) 11a (alone) la plus Ila (together) Infestation as a percentage of the infestation of the untreated control with a total concentration of active compound (in percent) of- Mixture ratio synergistic mixture required for the desired concentration of the active compound or synergistic mixture in the spray liquid is mixed with the stated amount of solvent, and the resulting concentrate is diluted with the stated amount of water which contains the stated emulsifier.

Young apple seedlings in the 4-6 leaf stage are sprayed with the particular spray liquid until dripping wet. The plants remain in a greenhouse for 24 hours at C. and at a relative atmospheric humidity of 70%. They are then inoculated with an aqueous conidium suspension of the apple scab organism (Fusicladium dendriticum and incubated for 18 hours in a humidity chamber at 18-20 C. and at a relative atmospheric humidity of 100%.

The plants then again are placed in a greenhouse for 14 days. 1 r

15 days after inoculation, the infestation of the seed- From Tables 1a, 1b, 1c and 2 it can. be seen clearly that the fungicidal effectiveness of the instant synergistic combination of active compounds is greater than the sum of the effects of the individual components.

In the various experiments above, the total concentration of active compounds in the combination are the same as the individual concentrations of active compounds when used alone rather than in combination. Hence it is to be expected that the effectiveness of the combinations should lie between that of the less effective individual component and that of the effective individual component. In fact, it is found that the combination of active compounds according to the invention has an effectiveness which lies far above the effectiveness of the most effective individual component.

This is demonstrated by the above experiments in which the degree of infestation, when the synergistic mixture composition according to the present invention is used, is less than the degree of infestation in the case of the most effective individual compound.

It will be realized by the artisan that the synergistic mixture combinations of the foregoing compounds contemplated by the present invention possess the desired strong fungicidal properties, with regard to a broad spectrum of activity, as well as a comparatively low toxicity toward warm-blooded creatures and a concomitantly low phytotoxicity, enabling such synergistic mixture of compounds to be used with correspondingly favorable compatibility with warm-blooded creatures and plants for more effective control and/or elimination of fungi by application of such synergistic mixture of compounds to such fungi and/ or their habitat.

It will be appreciated that the instant specification and examples are set forth by way of illustration and not limitation, and that various modifications and changes may be made without departing from the spirit and scope of the present invention.

What is claimed is:

l. Synergistic fungicidal composition which comprises a mixture of zinc propylene-1,2-bis-dithiocarbamate having the formula CH NH([l/S s and N-trichloromethylthiophthalimide having the formula N-SCCla in a ratio by weight of substantially between about 1:0.25-2.

2. Composition according to claim 1 wherein said dithiocarbamate and said phthalimide are in the ratio by weight of between about 1:0.5-2.

3. Composition according to claim 1 wherein said mixture is in the form of an overall mixture with a dispersible carrier vehicle, in which the first said mixture is present in a fungicidally effective amount.

4. Composition according to claim 3 wherein the combined content of said dithiocarbamate and said phthalimide in the first mixture is substantially between about 8 0.01 and by weight of the overall mixture with said dispersible carrier vehicle.

5. Composition according to claim 4 wherein said carrier vehicle is selected from the group consisting of (l) a dispersible finely divided carrier solid and (2) a dispersible carrier liquid containing a surface-active agent selected from the group consisting of anionic emulsifying agents, nonionic emulsifying agents, dispersing agents, and mixtures thereof.

6. Method for combating fungi, which comprises applying to at least one of (a) such fungi and (b) their habitat, a fungicidally effective amount of a fungicidal composition containing a mixture according to claim 1.

7. Method according to claim 6 wherein said dithiocarbamate and said phthalimide are in the ratio by weight of between about 1:0.5*2.

8. Method according to claim 6 wherein said mixture is in the form of an overall mixture with a dispersible carrier vehicle, in which the first said mixture is present in a fungicidally effective amount.

9. Method according to claim 8 wherein the combined content of said dithiocarbamate and said phthalimide in the first said mixture is substantially between about 0.01 and 95% by weight of the overall mixture with said dispersible carrier vehicle.

10. Method according to claim 9 wherein said carrier vehicle is selected from the group consisting of (l) a dispersible finely divided carrier solid and (2) a dispersible carrier liquid containing a surface-active agent selected from the group consisting of anionic emulsifying agents, nonionic emulsifying agents, dispersing agents, and mixtures thereof.

11. Method according to claim 6 wherein said fungicidal composition is applied in an amount such that said mixture is distributed in a dosage of substantially between about 1:0 and 10.0 kg. of said mixture per hectare.

12. Method according to claim 6 wherein said fungicidal composition is applied to a viticulture and fruiticulture habitat.

References Cited UNITED STATES PATENTS 5/1951 Kittleson 167-33 9/1967 Jung et al. 16713 US. Cl. X.R. 424-286 

